REACTION OF α-CHLOROTOLUENE WITH ELEMENTAL SULFUR IN LIQUID AMMONIA

Abstract

α-Chlorotoluene (1) reacts with elemental sulfur in liquid ammonia affording dibenzyl disulfide (2), dibenzyl trisulfide (3), dibenzyl tetrasulfide (4), dibenzyl pentasulfide (5) and benzylidene benzylimide (6) at a low temperature such as 20°C. This reaction is presumed to be initiated by the nucleophilic attack of ammonium thioaminohydroxylate, “H₂NS^-NH₄ ⁺,” or dithioaminohydroxylate, “H₂NSS^-NH₄,” formed upon treating elemental sulfur in liquid ammonia, on α-chlorotoluene (1). Benzylidene benzylimide (6) is presumed to be formed from benzylamine, which can be formed by treatment of α-chlorotoluene (1) with ammonia.     

Synthesis and Antimicrobial Activities of Some 6-Methyl-3-Thioxo-2,3-Dihydro-1,2,4-Triazine Derivatives

Abstract

4-Arylidene-imidazole derivatives (4a,b) were readily prepared by reacting 4-am- ino-6-methyl-3–thioxo-2,3–dihydro[1,2,4]triazin-5(4H)-one (1) with 4-arylidene-2-phenyl- 4H-oxazol-5-one (2). Reaction of 1 with some aromatic aldehydes in presence of triethylphosphite exclusively afforded the corresponding aminophosphonates 5a-c. Reaction of 1 with 3-phenyl-1H-quinazoline-2,4-dione (6a) and/or 3-phenyl-2-thioxo-2,3-dihydro- 1H-quinazolin-4-one (6b) gave 2-(6-methyl-5-oxo-3-thioxo-2,5-dihydro-3H-[1,2,4]triazin-4-ylimino)-3-phenyl-2,3-dihydro-1H-quinazolin-4-one (7). Moreover, on treating 1 with 2-phenylbenzo[d][1,3]thiazine-4-thione (8), 6-methyl-4-(2-phenyl-4-thioxo-4H-quinazolin-3-yl)-3-thioxo-3,4-dihydro-2H-[1,2,4]triazine-5-one (9) was obtained in 65% yield. Reaction of 1 with 4-sulfonylaminoacetic acid derivatives (10a,b) afforded the corresponding sulfonamides (11a,b), respectively. Acid hydrolysis of 11a afforded 7-aminomethyl-3-methyl[1,3,4]thiadiazole[2,3-c][1,2,4]triazin-4-one (12). 4-Amino-6-methyl-3-(morpholine-4-ylsulfanyl)-4H-[1,2,4]triazin-5-one (14) was prepared by reacting compound 1 with morpholine in presence of KI/I₂, while 3,3′-bis(4-amino-6-methyl-5-oxo-triazinyl)disulfide (16) was obtained by oxidation of 1 with lead tetraacetate. The antimicrobial activity of the products was evaluated against Gram-positive and Gram-negative bacteria as well as the fungus Candida albicans.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental files: Additional text, figures, and tables.]     

[2,2,2-TRIFLUOR-1-(2-HYDROXYPHENYL)ETHYL]-PHOSPHONSÄURE: MOLEKÜLSTRUKTUR VON [2,2,2-TRIFLUOR-1-(2-HYDROXYPHENYL)-ETHYL]DIMETHYLPHOSPHONAT

Abstract

The interaction of trimethylphosphite (1) and 2-trifluoroacetylphenol (2) yielded 4,5-benzo-2,2,2-trimethoxy-3-trifluoromethyl-1,2λ⁵[sgrave]⁵-oxaphosphol (3) and trimethylphosphate but not the expected 3-hydroxy derivative. Hydrolysis of compound 3 furnished the respective acyclic dimethylphosphonate 4 which was converted into the bis(trimethylsilyl)ester 5 and finally into the free phosphonic acid 6. O-trimethylsilylated compound 8 added to tris(trimethylsilyl)phospite (7) furnishing phosphonate 9 without abstracting the [sgrave]-oxygen. The molecular structure of 4 exhibited a somewhat distorted tetrahedral arrangement of substituents around phosphorus. An intermolecular hydrogen bridge O—H… O[dbnd]P was observed (O…O = 266.7 pm).     

3,3,3-Trifluoro-<Emphasis Type="Italic">N</Emphasis>′-(3-trifluoromethylphenyl)-1,2-propanediamine and its <Emphasis Type="Italic">N</Emphasis>-mono-and <Emphasis Type="Italic">N,N</Emphasis>-dicarboxyethyl derivatives: synthesis,protolytic and complexation properties

3,3,3-Trifluoro-N′-(3-trifluoromethylphenyl)-1,2-propanediamine (5) was synthesized by the reaction of 2-diazo-1,1,1-trifluoro-3-nitropropane or 3,3,3-trifluoro-1-nitropropene with 3-aminobenzotrifluoride followed by the reduction of the nitro group. The Michael 1,4-addition of diamine 5 to acrylic acid occurs only at the N(1) atom and affords N-mono-or N,N-dicarboxyethyl derivatives 6 and 7, depending on the reactant ratio. Protolytic equilibria 5–7 in aqueous solutions were studied by pH-potentiometry and UV spectroscopy. Only the aliphatic amino group can be protonated in an aqueous solution, while the aromatic amino group remains unprotonated even in 12 M HCl. The stability constants of transition metal (Cu²⁺, Ni²⁺, Zn²⁺) complexes with ligands 5–7 were determined by pH-potentiometric titration. The stability of the complexes and selectivity of the ligands toward Cu²⁺ ions increase with an increase in the number of N-carboxyethyl groups. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2465–2469, November, 2005.     

Solvothermal synthesis,structure, and luminescence of a 3-D Cd(II) complex assembled with biphenyl-2,5,2′,5′-tetracarboxylic acid involving in situ ligand reaction

A 3-D metal-organic framework [Cd₃(L)₂(DMF)₂]?·?2H₂O?·?2DMF (1) (H₃L?=?2-(dimethylcarbamoyl)biphenyl-5,2′,5′-tricarboxylic acid, DMF?=?N,N-dimethylformamide) with trinuclear Cd(II) units has been prepared. Complex 1 is a (3,?6)-connected (4²?·?6)₂(4⁴?·?6²?·?8⁸?·?10) coordination net, which results from the solvothermal in situ formation of a new asymmetric ligand, 2-(dimethylcarbamoyl)biphenyl-5,2′,5′-tricarboxylic acid (H₃L), through amidation of biphenyl-2,5,2′,5′-tetracarboxylic acid (H₄bptc). Additionally, the luminescence of 1 has been investigated.     

Dialkyl (Alkylene) Dithiophosphate Adducts of Anhydrous Stannous Chloride: Synthesis,Characterization, and Biological Activities

Abstract

Dialkyl (alkylene) dithiophosphate adducts of stannous chloride were synthesized by the reaction of anhydrous tin(II) chloride (SnCl₂) and dialkyl (alkylene) dithiophosphoric acid in a 1:1 molar ratio, under anhydrous reaction conditions, below 5 °C in a closed vessel. The newly synthesized adducts were characterized by physicochemical and spectroscopic techniques [FT-IR, NMR (¹H, ³¹P, and ¹¹⁹Sn), and mass spectrometry]. Coordination modalities have indicated a donor–acceptor interaction between sulfur and tin(II) moieties, where tin(II) acts as a Lewis acid. The adducts were found to have significant antibacterial activity against Escherichia coli and Pseudomonas aeruginosa, and antifungal activity against Aspergillus niger and Candida albicans.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

A Simple Synthesis of Dimethylphosphinyl-Substituted Tetrahydropyrroles

Abstract

New dimethylphosphinyl-substituted tetrahydropyrroles 3, 5, 6 and 8 have been synthesized via 1,3-cycloaddition reaction of the N-(4-chlorophenylmethylene)aminomethyl-dimethylphosphinoxide (1) to benzylideneacetophenone, ethyl cinnamate and cinnamonitrile. The structure of the compounds was confirmed by elemental analysis, IR, ¹H-, and ³¹P¹H-NMR spectroscopy and in some cases by mass spectrometry, as well.     

Ein Beitrag zur Chemie des 2,3-Dihydro-3-oxo-benzo[b]thiophen-1,1-dioxids Synthesen mit Nitrilen, 86. Mitt.

Summary 2,3-Dihydro-3-oxo-benzo[b]thiophen-1,1-dioxide (1) reacts as CH-acidic component with amidines of orthoesters and anilines resp. to give the anilinomethylene derivates3, 4, and5. With triethyl orthoformiate the hydroxymethylene-compound7 is obtained. Anilino- and phenylhydrazino derivates8 and9 prove the carbonyl activity of1, azo-coupling leads to10, whereas treatment of1 with sulfur and malononitrile yields the benzo[b]thieno[2,3-d]thiophenes11. Introduction of substituents with active NH-functions in position 2 of the dicyanomethylene-product2, such as azocoupling, reaction with phenyl isocyanate and formation of enamines, leads to ring closure reactions between a nitrile and the NH-group. Thereby the phenyl-benzo[4,5]thieno[2,3-c]pyridazines12, the phenyl-1H-benzo[4,5]thieno[2,3-c]pyridines13 and the phenylamino-benzo[4,5]thieno[2,3-c]pyridines14 are obtained.¹³C and¹⁵N-NMR spectroscopy was used as proof of the ring closure reactions.

     

Crystal Structure and Spectroscopic Properties of (2-oxo-2H-chromen-3-yl)phosphonic Acid Monoethyl Ester Trihydrate

Abstract

(2-Oxo-2H-chromen-3-yl)phosphonic acid monoethyl ester trihydrate (1) was synthesized, isolated, and spectroscopically as well as structurally characterized by means of single crystal X-ray diffraction; conventional and linear-polarized IR spectroscopy; electronic (UV-VIS-NIR) spectroscopy; ¹H, ¹³C, and ³¹P NMR. Quantum chemical DFT calculations have been performed in order to obtain information on the electronic structure and vibrational properties of 1, thus supporting the experimental data. The correlation between the structure and spectroscopic characteristics is discussed.

GRAPHICAL ABSTRACT      

Unusual regioselective acylation of the primary hydroxy groups of β-cyclodextrin

The reaction of -cyclodextrin (1) with palmitoyl (2) and valeryl (4) chlorides in DMF or Py, unlike previously studied acetylation of 1, involves only the primary hydroxy groups of 1. The outcome of the reaction depends on the reaction conditions and the nature of the acid scavenger used (Et₃N, Prⁱ ₂NEt, PhNMe₂, Py). ¹³C NMR spectroscopy was shown to be an effective tool in determining the number and position of aliphatic carboxylic acid residues introduced into 1. A hypothesis stating that preliminary formation of a reactive inclusion complex (acid chloride1) is required for the acylation of 1 to occur is proposed and substantiated. This hypothesis provides a unified explanation for a variety of unusual facts observed in the acylation of 1 and its derivatives.     

Darstellung und Kristallstruktur der Addukte [DB-18C6] · CH3CN · CH3CSOH und [DC-18C6](CH3CSOH)2 sowie der salzartigen Verbindungen [Cs(B-15C5)2]CH3CSS und [Cs(DB-18C6)]2S5(DMF)21)

Synthesis and Crystal Structure of the Adducts [DB-18C6] · CH₃CN · CH₃CSOH and [DC-18C6](CH₃CSOH)₂ as well as of the Salt-like Compounds [Cs(B-15C5)₂]CH₃CSS and [Cs(DB-18C6)]₂S₅(DMF)₂¹) The reaction products of crown ethers, cesium, and sulfur in aprotic solvents like acetonitrile and dimethylformamide strongly depend on the reaction conditions. Using CH₃CN as a solvent, sometimes neutral host-guest adducts crystallize only, e.g., [dibenzo-18C6] · CH₃CN · CH₃CSOH (monoclinic, S. G. P2₁/c, Z = 4, a = 9.73(1) Å, b = 22.03(1) Å, c = 11.86(1) Å, β = 91.8(1)°) or [dicyclohexyl-18C6](CH₃CSOH)₂ (monoclinic, S. G. P2₁/n, Z = 2, a = 7.75(1) Å, b = 10.32(1) Å, c = 17.73(1) Å, β = 95.7(1)°). The monothioacetic acid, CH₃CSOH, must be regarded as the first product of the hydrolysis of CH₃CN. Furthermore, another product of this kind of hydrolysis, CH₃CSSH, is obtained too. Therefore, we also obtain the salt-like compound [Cs(benzo-15C5)₂]CH₃CSS (monoclinic, S. G. C2/c, Z = 4, a = 16.05(1) Å, b = 16.73(1) Å, c = 13.11(1) Å, β = 106.3(1)°). If the solvent DMF is used, the pentasulfide [Cs(dibenzo-18C6)]₂S₅(DMF)₂ crystallizes (monoclinic, S. G. P2₁/n, Z = 4, a = 14.79(1) Å, b = 14.24(1) Å, c = 25.74(1) Å, β = 92.7(1°. The S₅^2? anions show the cis-conformation.     

Crystal structures,selective fluorescent sensing and photocatalytic properties of cobalt(II) and copper(II) coordination architectures with 2,4,5-tri(4-pyridyl)-imidazole

Abstract

Solvothermal reaction of M^II (M?=?Co, Cu) ions with 2,4,5-tri(4-pyridyl)-imidazole (Htpim) gave two MOFs, [Co_1.5(tpim)(FA)₂(H₂O)]_n (1) and [Cu₂(Htpim)(tpim)(FA)(NO₃)₂(DMF)]_n (2) (HFA?=?formic acid, DMF?=?N,N-dimethylformamide). Single-crystal X-ray diffraction analyses indicated that 1 exhibits a 3D {4³.4¹²} topology framework assembled by hexanuclear [Co₆(FA)₈(H₂O)₄] units and tpim ligands, while 2 presents a 2-D double layer {4.6²}₂{4².6⁴.8².10²}{6².8} network. Hereinto, an inorganic acid was not only used to adjust the pH value of reaction system but also to act as an oxidizing agent to participate in in situ organic reactions. Moreover, 1 displays high sensitivity in the detection of nitrobenzene as a fluorescent sensor and exhibits a relatively good photocatalytic activity toward the degradation of rhodamine B in aqueous solution under UV irradiation.     

Gemeinsame Einwirkung von elementarem Schwefel und Äthylenimin auf Ketone, 3. Mitt.: Über die gemeinsame Einwirkung von elementarem Schwefel und gasförmigem Ammoniak auf Ketone, 74. Mitt.

Zusammenfassung Bei der Einwirkung von Äthylenimin und Schwefel auf Methyläthylketon, Methylisopropylketon und Äthylisopropylketon entstehen strukturisomere 5,6-Dihydro-1,4-thiazine (1–6) und als Nebenprodukte die dem jeweiligen Keton entsprechenden Thiazolidine (7–9).Die 5,6-Dihydro-1,4-thiazine werden mit Ameisensäure in N-Formylthiomorpholine (10–15) übergeführt, die mit verd. HCl glatt zu den entsprechenden Thiomorpholinen (16–21) hydrolysiert werden.Das Verhältnis der Thiomorpholin-Isomerenpaare wird gaschromatographisch quantitativ bestimmt.

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Concomitant action of elementary sulfur and gaseous ammonia upon ketones, LXXIV: Concomitant action of elementary sulfur and ethylenimine upon ketones, III

The reaction of ethylenimine and sulfur with methyl ethyl ketone, methyl isopropyl ketone and ethyl isopropyl ketone, resp., yields the structurally isomeric 5.6-dihydro-1.4-thiazines (1–6) and as by-products the thiazolidines (7–9) derived from the corresponding ketones.The 5.6-dihydro-1.4-thiazines are converted with formic acid to the N-formyl thiomorpholines10–15, which are easily hydrolyzed with dilute hydrochloric acid to the corresponding thiomorpholines (16–21). The ratio of the pairs of structurally isomeric thiomorpholines is determined by quantitative gas chromatography.

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2. Mitt.:F. Asinger, H. Offermanns, K. H. Lim undD. Neuray, Mh. Chem.101, 1281 (1970).

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73. Mitt.:F. Asinger, H. Offermanns undD. Neuray, Ann. Chem.739, 72 (1970).

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Teil der DissertationK. H. Lim, Techn. Hochschule Aachen, 1969.     

Phenyl-functionalized diiron propanediselenolato complexes containing the chelated or bridged 1,3-bis(diphenylphosphine)propane ligand

Abstract

Reaction of precursor Fe₂[(μ-SeCH₂)₂CHC₆H₅](CO)₆ (A) with 1,3-bis(diphenylphosphine)propane (dppp) in refluxing xylene yielded one diphosphine-containing complex Fe₂[(μ-SeCH₂)₂CHC₆H₅](CO)₄(κ²-dppp) (1) with the diphosphine of dppp displacing the apical and one basal carbonyl ligands of a single iron center, while treatment of precursor A with one-half equivalent of dppp in MeCN in the presence of Me₃NO·2H₂O gave another diphosphine-containing complex {Fe₂[(μ-SeCH₂)₂CHC₆H₅](CO)₅}₂(μ,κ¹,κ¹-dppp) (2) with the diphosphine of the dppp bridging two diiron diselenolato clusters upon replacing one of basal carbonyls, respectively. The structures of both complexes were fully characterized by spectroscopic methods and X-ray crystallography. The electrochemical behaviors of both complexes were investigated by cyclic voltammetry (CV) and the electrochemical reduction of protons from acetic acid to give dihydrogen catalyzed by complex Fe₂[(μ-SeCH₂)₂CHC₆H₅](CO)₄(κ²-dppp) was observed.     

Tetranuclear cobalt(II) complex and trinuclear copper(II) complex with the ligand 2-hydroxy-3-[(2-sulfoethylimino)-methyl]-benzoic acid: synthesis,structure and properties

A cobalt(II) compound, [Co₄(L)₂(OH)₂(phen)₂(H₂O)₄] · 6H₂O (1), and a copper(II) compound, [Cu₂(L)₂(H₂O)₂][Cu(H₂O)₆] · 6H₂O (2) [where H₃L is 2-hydroxy-3-[(2-sulfoethylimino)-methyl]-benzoic acid and phen is O-phenanthroline], were prepared and characterized. The tetranuclear cobalt complex 1, C₄₄H₆₂N₆O₂₈S₂Co₄, crystallizes in the monoclinic space group P2₁/c, with a = 11.847(10) Å, b = 19.061(15) Å, c = 12.635(10) Å, β = 105.483(9)°, and Z = 2; R ₁ for 4821 observed reflections [I > 2σ(I)] was 0.0679. Complex 1 is a centrosymmetric tetranuclear cobalt complex with all cobalts having distorted octahedral geometry. The molecule can be viewed as two planar [Co₂(OH)(L)(Phen)H₂O] units tied together by two terminal water molecules. The framework of 1 has the appearance of two connected face-sharing cubes, each with one vertex missing. The trinuclear copper complex 2, C₂₀H₄₄Cu₃N₂O₂₆S₂, crystallizes in the triclinic space group P1, with a = 7.524(1) Å, b = 7.902(2) Å, c = 16.885(4) Å, α = 88.993(6)°, β = 80.725(7)°, γ = 66.725(4)° and Z = 1; R ₁ for 4298 observed reflections [I > 2σ (I)] was 0.0360. Complex 2 is an ionic compound, in which the three Cu(II) centers have two coordination modes. The molecule has a centrosymmetric dinuclear copper coordinated anion and a hexa-aqua-copper cation. The sulfonic acid group has less coordination ability than carboxylate oxygen.     

基于3，4'，5-联苯三羧酸构筑的钕配合物的合成、结构、荧光、光催化及磁性质

采用NdCl₃·6H₂O和3,4'',5-联苯三羧酸（H₃bpt）为原料在DMF/H₂O混合溶剂热条件下合成得到一个三维钕配合物{[Nd （bpt）（DMF）（H₂O）]·2H₂O}_n（1）,并通过红外光谱、元素分析、单晶及粉末X射线衍射表征了配合物1的结构。单晶衍射结果表明,配合物1具有（5,5）-连接的三维结构,拓扑符号为（4⁴·6³·8³）（4⁸ 6²）。此外,对配合物1的热稳定性、荧光性质、光催化降解染料及磁性质进行了详细研究。     

TRITHIA-DIPHOSPHABIYCLO[2.2.1]HEPTANE

Abstract

3,6-Dialkyl-2,5-Dithioxo-1,4,2λ⁵,5λ⁵-dithiadiphosphorinan-2,5-disulfides (1) react with PSCI₃, to give 3,6-Dialkyl(diaryl)-1,4-dithioxo-2,5,7-trithia-lλ⁵,4λ⁵ diphosphabicyclo[2.2.1]heptanes (2). The reaction mechanism of their formation. and the stereochemistry are discussed. By reduction of 2 with (n-C₄H₉)₃P or (C₆H₅),P 3,6-Dialkyl-2,5,7-trithia-1λ³,4λ³-diphosphabicyclo[2.2.1]heptanes (3) are formed. 2c reacts with one mole of (C₆H₅)₃P to give 3,6-Diethyl-l-thioxo-2,5,7-trithia-lλ⁵,4λ³- diphosphabicyclo(2.2.1]heptane, 4c.

3,6-Dialkyl-2,5-dithioxo-1.4,2λ⁵,5λ⁵-dithiadiphosphorinan-2,5-disulfide (I) reagieren mit PSCI₃ zu 3,6-Dialkyl(diaryl)-1,4-dithioxo-2,5,7-trithia-lλ⁵,4λ⁵-diphosphabicyclo[2.2.l]heptanen (2). Der Reaktionsmechanismus ihrer Bildung und ihre Stereochemie werden diskutiert. Die Reduktion von 2 mit (n-C₄H₉)₃,P oder (C₆H₅)₃P führt zu 3,6-Dialkyl-2,5,7-trithia-1λ³,4λ³-diphosphabicyclo[2.2.1] heptanen(3). 2c reagiert mit einer äquimolaren Menge (C₆H₅)₃,P zu 3,6-Diethyl-l-thioxo-2,5,7-trithia-lλ⁵,4λ³- diphosphabicyclo[2.2.1]heptan, 4c.     

Functionally Substituted N- and P-Containing Salts of Resinous and Bile Acids

New functionally substituted N- and P-containing salts of resinous and bile acids 1b, c, 2b-f, 3b-f, 4b-f, 5b, c, and 6b, c were prepared by reaction of the corresponding acids with amines or triphenylphosphine in anhydrous acetone.     

13,17,53,57-Tetraphenyl-13,17,53,57-tetrathio-3,7-dithia-1,5(1,5)-di(1,5-diaza-3,7-diphosphacyclooctana)-2,4,6,8(1,4)-tetrabenzenacyclooctaphane with an unusual conical-like conformation

1³,1⁷,5³,5⁷-tetraphenyl-1³,1⁷,5³,5⁷-tetrathio-3,7-dithia-1,5(1,5)-di(1,5-diaza-3,7-diphosphacyclooctana)-2,4,6,8(1,4)-tetrabenzenacyclooctaphane 2b was obtained by sulfurization of the corresponding macrocyclic tetraphosphine 1b. The structure of the inclusion complex of tetrasulfide 2b with DMF was investigated by the X-ray crystal structure analysis. A novel for this type of cyclophanes and relatively rare conical-like conformation of the macrocycle was found. A methyl group from one of the solvating DMF molecules penetrates the macrocyclic cavity of 2b from the side of the wider rim. According to quantum-chemical simulations, this may be the reason of the unusual conical conformation of 2b because the cavity of the macrocycles of this type is highly flexible. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.